In: Journal of the American Chemical Society, 2007, vol. 129, no. 11, p. 3211 -3217
A new method for investigating the mechanisms of nitric oxide release from NO donors under oxidative and reductive conditions is presented. Based on the fragmentation of N-nitrosoamines, it allows generation and spectroscopic characterization of nitrenium cations, amide anions, and aminyl radicals. X-irradiation of N-nitroso-N,N-diphenylamine 1 in Ar matrices at...
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In: The Journal of Physical Chemistry A, 2006, vol. 110, no. 3, p. 1163 -1170
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In: Journal of the American Chemical Society, 2006, vol. 128, no. 24, p. 7828 -7834
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In: The Journal of Physical Chemistry A, 2007, vol. 111, no. 9, p. 1667 -1676
The first few bands in the optical spectra of radical cations can often be interpreted in terms of A-type transitions that involve electron promotions from doubly occupied to the singly occupied molecular orbital (SOMO) and/or B-type transition which involve electron promotion from the SOMO to virtual molecular orbitals. We had previously demonstrated that, by making use of Koopmans' theorem, the...
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In: The Journal of Organic Chemistry, 2006, vol. 7, no. 14, p. 5312 -5319
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In: Angewandte Chemie International Edition, 2006, vol. 45, no. 40, p. 6616 - 6619
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In: Chemistry - A European Journal, 2006, vol. 12(17), p. 4559-4567
Three tricyclic vinylcyclobutanes (3-methylenetricyclo[5.3.0.02,6]decanes 1-3) have been subjected to ionization by photoinduced electron transfer in solution and by X-irradiation in Ar matrices. All three compounds undergo oxidative cycloreversion; the cleavage of the four-membered ring, however, occurs in a different direction depending on the presence of a methyl group...
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In: Physical Chemistry Chemical Physics, 2006, vol. 8, p. 719-727
The photochemistry of p-azidoaniline was studied in argon matrices in the absence and presence of oxygen. With the help of quantum chemical calculations we were able to characterize the triplet p-aminophenylnitrene as well as the cis- and trans-p-aminophenylnitroso oxides. It was found that the latter two isomers can be interconverted by selective...
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In: ChemPhysChem, 2006, vol. 7(6), p. 1268-1275
2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence of...
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In: Chemistry - A European Journal, 2005, vol. 11(4), p. 1294-1304
Radical cations were generated from different phenyl-substituted aziridines by pulse radiolysis in aqueous solution containing TlOH.+, N₃. or SO₄.- as oxidants or in n-butyl chloride, by ⁶⁰Co γ radiolysis in Freon matrices at 77 K, and in some cases by flash photolysis in aqueous solution. Depending on the substitution pattern of the aziridines, two...
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